CN110038634B - A kind of oxygen evolution reaction catalyst based on the composite structure of MXene and metal organic framework compound and its synthesis method - Google Patents
A kind of oxygen evolution reaction catalyst based on the composite structure of MXene and metal organic framework compound and its synthesis method Download PDFInfo
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Abstract
一种基于MXene与金属有机骨架化合物复合结构的析氧反应催化剂及其合成方法，属于纳米材料、能源与催化领域。该催化剂由表面均匀负载MOFs纳米颗粒的MXene二维纳米薄片组成，具有二维结构。制备方法：将MXene、金属盐、有机配体和缚酸剂溶解混合均匀后，离心、洗涤、真空干燥，获得结构、成分可精细调控的二维纳米结构的电催化剂。本发明获得的电催化剂可有效克服MOFs导电性差、稳定性差而导致析氧反应催化性能无法发挥的基础性难题；所得催化剂在碱性电解液中对析氧反应表现出优异的催化活性与稳定性，为燃料电池、金属空气电池、电解水等新能源技术的广泛应用奠定基础。
An oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound and a synthesis method thereof belong to the fields of nanomaterials, energy and catalysis. The catalyst consists of MXene 2D nanosheets with MOFs nanoparticles loaded uniformly on the surface, and has a 2D structure. Preparation method: after dissolving and mixing MXene, metal salt, organic ligand and acid binding agent uniformly, centrifuging, washing and vacuum drying to obtain a two-dimensional nanostructured electrocatalyst whose structure and composition can be finely regulated. The electrocatalyst obtained by the invention can effectively overcome the basic problem that the MOFs have poor conductivity and poor stability, which lead to the inability to exert the catalytic performance of the oxygen evolution reaction; the obtained catalyst exhibits excellent catalytic activity and stability for the oxygen evolution reaction in an alkaline electrolyte , laying the foundation for the wide application of new energy technologies such as fuel cells, metal-air batteries, and electrolyzed water.
Description
Technical Field
The invention belongs to the field of nano materials, energy and catalysis, and relates to an oxygen evolution reaction catalyst based on a MXene and metal organic framework compound composite structure and a synthesis method thereof.
Background
Fuel cells, metal air cells, electrolytic water, etc. which use Oxygen Evolution Reaction (OER) as a core reaction are one of the most promising new renewable energy storage and conversion technology systems at present. The oxygen evolution reaction involves a four-electron transfer process, the reaction energy barrier is high, the process kinetic rate is slow, and a high-efficiency catalyst needs to be used to improve the energy conversion efficiency. RuO2And IrO2Etc. are the best active catalysts at present, but the scarce resources and high costs limit their scaleAnd (5) chemical application. The development of cheap, efficient and stable non-noble metal oxygen evolution reaction catalyst is one of the key bottleneck problems for promoting the new energy technologies such as fuel cells, metal air cells, water electrolysis and the like to be practically applied.
Metal-Organic Frameworks (MOFs) are a class of three-dimensional ordered network porous crystal materials formed by transition Metal ions and Organic ligands through coordination bonds, and have the advantages of high porosity, large specific surface area, adjustable pore diameter and the like. The high controllability of metal central elements and organic ligands in the MOFs structure on the chemical composition endows the MOFs structure with various unique properties, and the MOFs structure has wide application prospects in the fields of energy storage and conversion, catalysis, sensors, gas separation and the like. However, the application of MOFs in the field of electrochemical catalysis is still greatly limited by its poor electrical conductivity and structural stability, and the development of high-performance oxygen evolution reaction catalysts based on MOFs still faces a great challenge.
MXene is a new kind of two-dimensional crystal material of transition metal carbide or nitride. Having the chemical formula Mn+1XnTx(n ═ 1, 2, 3, M is a transition metal element, X is a carbon or nitrogen element, and T is a chemical group), can be obtained by selective etching of the phase of the laminar ceramic material MAX. MXene surface is rich in active chemical functional groups such as-OH, -F, -O and the like, and simultaneously has excellent conductivity of metalloid, so that MXene can be expected to be used as an ideal conductive and active matrix to comprehensively improve the conductivity and the reaction activity of MOFs materials, and the creation and controllable construction of a new structure and high-performance oxygen evolution reaction catalyst based on MOFs are realized.
Disclosure of Invention
Aiming at the defects of poor conductivity, poor structural stability and the like of MOFs, the invention provides an oxygen evolution reaction catalyst based on an MXene and MOFs composite structure and a synthesis method thereof, and the prepared catalyst consists of MXene two-dimensional nano sheets with MOFs nano particles uniformly loaded on the surfaces. The introduction of the high-conductivity MXene and the uniform loading of the MOFs nano thin layer on the MXene surface overcome the fundamental problem that the catalytic performance of the oxygen evolution reaction cannot be exerted due to poor conductivity and poor stability of the MOFs, and the obtained catalyst shows excellent catalytic activity and stability in the electrochemical oxygen evolution reaction process under the alkaline condition. The synthesis method is green and environment-friendly, low in energy consumption, easy to control and universal, and can be used for large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound is composed of MXene two-dimensional nano sheets with MOFs nano particles uniformly loaded on the surfaces, has a two-dimensional structure, and has the size of between 100 and 500 nm; the content of MOFs nano particles loaded on MXene is more than 75 wt%, the size of the MOFs nano particles is 10-100nm, and metal elements in the MOFs comprise at least one or more of nickel, iron, cobalt and manganese. The obtained catalyst has excellent catalytic activity and stability for oxygen evolution reaction under alkaline condition.
A synthetic method of an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound comprises the following steps:
1) MXene was dispersed in water at normal temperature and pressure to prepare a dispersion.
The concentration of the MXene dispersion liquid is 5-15mg mL-1。
2) Dissolving metal salt and organic ligand in a mixed solvent of N, N-Dimethylformamide (DMF) and ethanol at normal temperature and pressure to form a uniform solution.
The molar ratio of the metal salt to the organic ligand is 1:1, and the concentration of the organic ligand is 0.0375-0.04 mol/L.
The organic ligand is at least one of terephthalic acid and 2-amino terephthalic acid.
In the mixed solvent, the volume ratio of DMF to ethanol is 5:1-15: 1.
The metal salt is one, any two or any three combination of nickel salt, iron salt, cobalt salt and manganese salt, wherein the nickel salt, the iron salt, the cobalt salt and the manganese salt all comprise chloride salt, nitrate and acetate. When two metal salts are used, the molar ratio of the two different cationic metal salts is from 5:1 to 1: 5; when three metal salts are used, the molar ratio of the three different cationic metal salts is 1:1: 1.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand uniform solution prepared in the step 2) at normal temperature and normal pressure.
4) Adding triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, stirring and reacting for 2-4h, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
The volume ratio of the triethylamine to the mixed solution is as follows: 1:20-68.
Compared with the prior art, the invention solves the problems of preparation and application of the MOFs-based oxygen evolution reaction catalyst, and has the following beneficial effects:
1) MXene with excellent metalloid conductivity is introduced to remarkably improve the conductivity of MOFs, so that the catalytic activity of the MOFs on oxygen evolution reaction is fully exerted.
2) MXene chemical coupling with rich surface active chemical functional groups is introduced, MOFs is efficiently and stably stabilized, and the obtained composite nano-catalyst has excellent catalytic stability.
3) MXene with a two-dimensional nanostructure is introduced to be combined with the MOFs nanostructure, and the obtained two-dimensional nanostructure composite nano catalyst has an electrode-electrolyte-oxygen three-phase reaction interface and an electrochemical reaction active surface area which are larger than those of a block MOFs material, and exposes more catalytic reaction active sites, so that the catalytic reaction activity of the composite nano catalyst is synergistically improved.
4) The invention can realize the fine regulation and control of the microstructure, the chemical composition and the like of the oxygen evolution reaction catalyst based on the MXene and MOFs composite nano structure. The process is simple, environment-friendly and easy for large-scale production, and has wide application prospect in the fields of energy storage and conversion application such as fuel cells, full-electrolysis water, metal-air batteries and the like.
Drawings
FIG. 1 is a scanning electron microscope photomicrograph of a non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the invention;
FIG. 2 is a TEM photograph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiCo-BDC MOFs prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiMn-BDC MOFs prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope photomicrograph of a non-noble metal composite nanocatalyst based on MXene and NiFeMn-BDC MOFs prepared in example 5 of the present invention;
FIG. 6 is the characterization of the catalytic activity of the non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the present invention on oxygen evolution reaction and its reaction with commercial RuO2Comparing the activity of the catalysts;
FIG. 7 is a graph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention for stability characterization of oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst stability.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention, and further explains the technical solution, the implementation process and the principle, etc. as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation method of composite nanocatalyst based on MXene and NiFe-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)1.0mmol of nickel acetate, 0.2mmol of ferric nitrate and 1.2mmol of terephthalic acid are dissolved in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 0.8mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 2 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiFe-based MOFs nanoparticles having a size of about several nanometers with a loading of about 88.0 wt.%.
Example 2 preparation method of composite nanocatalyst based on MXene and NiCo-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 5 mg/mL solution-1The dispersion of (1);
2) dissolving 0.6mmol of nickel chloride, 0.6mmol of cobalt chloride and 1.2mmol of terephthalic acid in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 0.5mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 2 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nano-sheets with the average size of about 100-500nm and loaded with NiCo-based MOFs nanoparticles with the size of about several nanometers and the loading of about 94.0 wt.% are obtained.
Example 3 preparation method of composite nanocatalyst based on MXene and NiMn-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of solution with a concentration of 15mg mL-1The dispersion of (1);
2) dissolving 0.2mmol of nickel acetate, 1.0mmol of manganese nitrate and 1.2mmol of terephthalic acid in 28mL of N, N-Dimethylformamide (DMF) and 4mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 4 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiMn-based MOFs nanoparticles having a size of about several nanometers with a loading of about 80.0 wt.%.
Example 4 preparation of composite nanocatalysts based on MXene and Ni-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of solution with a concentration of 15mg mL-1The dispersion of (1);
2)1.2mmol of nickel chloride and 1.2mmol of terephthalic acid are dissolved in 28mL of N, N-Dimethylformamide (DMF) and 4mL of ethanol at normal temperature and pressure to form a uniform solution;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 3 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with Ni-based MOFs nanoparticles having a size of about several nanometers with a loading of about 78.0 wt.%.
Example 5 preparation of composite nanocatalysts based on MXene and NiFeMn-BDC MOFs
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)0.4mmol of nickel acetate, 0.4mmol of ferric chloride, 0.4mmol of manganese nitrate and 1.2mmol of terephthalic acid were dissolved in 25mL of N, N-Dimethylformamide (DMF) and 5mL of ethanol at normal temperature and pressure to form a uniform solution.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.5mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 4 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 150-500nm loaded with NiFeMn-based MOFs nanoparticles having a size of about several nanometers with a loading of about 92.0 wt.%.
Example 6 based on MXene and NiFe-BDC-NH2Preparation method of MOFs composite nano-catalyst
1) MXene was dispersed in water at room temperature under normal pressure to prepare 2mL of 10 mg/mL solution-1The dispersion of (1);
2)1.0mmol of nickel acetate, 0.2mmol of ferric nitrate and 1.2mmol of 2-amino terephthalic acid were dissolved in 30mL of N, N-Dimethylformamide (DMF) and 2mL of ethanol at room temperature under normal pressure to form a homogeneous solution.
3) Uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand solution prepared in the step 2) at normal temperature and normal pressure;
4) adding 1.0mL of triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, reacting for 3 hours under the stirring condition, centrifugally washing by using ethanol after the reaction is finished, and then drying in vacuum.
Two-dimensional nanosheets were obtained having an average size of about 100-500nm loaded with NiFe-based MOFs nanoparticles having a size of about several nanometers with a loading of about 89.0 wt.%.
FIG. 6 is the characterization of the catalytic activity of the non-noble metal composite nano-catalyst based on MXene and NiFe-BDC MOFs prepared in example 1 of the present invention on oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst activity. The test is carried out in a three-electrode system, 1M KOH is used as electrolyte, and a working electrode is loadedThe composite nano catalyst based on MXene and NiFe-BDC MOFs comprises an Ag/AgCl electrode as a reference electrode, a platinum sheet as a counter electrode and a scanning rate of 10mV s-1The electrochemical workstation was CHI 760E. As can be seen, the catalyst obtained by the invention only needs 268mV overpotential to reach 10mA cm-1Current density of (2), while RuO is commercialized2The overpotential required for the catalyst to reach the same current density was 378 mV. Therefore, the catalytic activity of the catalyst obtained by the invention on oxygen evolution reaction in alkaline electrolyte is superior to that of commercial noble metal RuO2A catalyst.
FIG. 7 is a graph of MXene and NiFe-BDC MOFs-based non-noble metal composite nanocatalysts prepared in example 1 of the present invention for stability characterization of oxygen evolution reaction and its reaction with commercial RuO2Comparison of catalyst stability. The test is carried out in a three-electrode system, 1M KOH is used as electrolyte, a working electrode is loaded with a composite nano catalyst based on MXene and NiFe-BDC MOFs, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the scanning rate is 10mV s-1The electrochemical workstation was CHI 760E. As can be seen from the figure, the catalyst obtained by the invention has the current density of 10mA cm-1While the voltage can be kept stable for 23h, RuO is commercialized2The catalyst rapidly rises in voltage under the same current density, and becomes invalid after 3 hours. Therefore, the stability of the catalyst obtained by the invention on oxygen evolution reaction in alkaline electrolyte is better than that of commercial noble metal RuO2A catalyst.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A synthetic method of an oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound is characterized by comprising the following steps:
1) dispersing MXene in water at normal temperature and pressure to prepare a dispersion liquid;
2) dissolving metal salt and organic ligand in a mixed solvent of N, N-dimethylformamide DMF and ethanol at normal temperature and pressure to form a uniform solution; the molar ratio of the metal salt to the organic ligand is 1:1, and the concentration of the organic ligand is 0.0375-0.04 mol/L; the organic ligand is at least one of terephthalic acid and 2-amino terephthalic acid; the metal salt is at least one or more than two of chloride, nitrate and acetate of nickel, iron, cobalt and manganese;
3) uniformly mixing the MXene dispersion liquid prepared in the step 1) with the metal salt/organic ligand uniform solution prepared in the step 2) at normal temperature and normal pressure;
4) adding triethylamine serving as an acid-binding agent into the mixed solution prepared in the step 3) under the conditions of normal temperature and normal pressure, stirring and reacting for 2-4h, centrifugally washing by using ethanol after the reaction is finished, and drying in vacuum to obtain a product.
2. The method for synthesizing the catalyst for oxygen evolution reaction based on the compound structure of MXene and metal organic framework compound of claim 1, wherein the concentration of MXene dispersion in step 1) is 5-15mg mL-1。
3. The method for synthesizing the catalyst for oxygen evolution reaction based on the composite structure of MXene and metal organic framework compound according to claim 1, wherein the volume ratio of DMF and ethanol in the mixed solvent of step 2) is 5:1-15: 1.
4. The method for synthesizing the catalyst for oxygen evolution reaction based on the compound structure of MXene and metal organic framework compound as claimed in claim 1, wherein in step 2), when two metal salts are used, the molar ratio of two different cationic metal salts is 5:1-1: 5; when three metal salts are used, the molar ratio of the three different cationic metal salts is 1:1: 1.
5. The method for synthesizing the catalyst for oxygen evolution reaction based on the composite structure of MXene and metal organic framework compound according to claim 1, wherein the volume ratio of the triethylamine in the step 4) to the mixed solution is as follows: 1:20-68.
6. An oxygen evolution reaction catalyst based on a composite structure of MXene and a metal organic framework compound, which is obtained by the synthesis method of any one of claims 1 to 5, wherein the catalyst consists of MXene two-dimensional nano flakes with MOFs nano particles uniformly loaded on the surface, has a two-dimensional structure, and has the size of 100-500 nm; the content of MOFs nano particles loaded on MXene is more than 75 wt%, the size of the MOFs nano particles is 10-100nm, and metal elements in the MOFs comprise at least one or more of nickel, iron, cobalt and manganese; the obtained catalyst has excellent catalytic activity and stability for oxygen evolution reaction under alkaline condition.
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| CN110589786A (en) * | 2019-10-16 | 2019-12-20 | 大连理工大学 | Three-dimensional porous transition metal carbide Ti3C2MXene composite nanostructure and its general preparation method |
| CN111151304A (en) * | 2020-02-26 | 2020-05-15 | 吴晓峰 | Preparation of three-dimensional MXene/MOF hydrogel and application thereof in water treatment |
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